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During processing and storage of both conventional and lactose-hydrolyzed UHT milk (LHM), aggregation of milk proteins occurs. Protein aggregation can inter alia occur via non-reducible covalent cross-links derived from either Maillard or dehydroalanine (DHA) pathways. To study this further in relation to processing method and lactase enzyme purity, LHM was produced using 3 different lactase preparations, with lactase enzymes added in a dairy setting either before (pre-hydrolysis) or after (post-hydrolysis) UHT treatment. The prepared LHM types were subsequently stored at either 25°C or 35°C for up to one year. Mass spectrometry was used to absolutely quantify the level of furosine, N-ɛ-(carboxymethyl)lysine (CML) and N-ɛ-(carboxyethyl)lysine (CEL), lanthionine (LAN) and lysinoalanine (LAL) in these products using a newly developed method on Triple Q for these processing-induced markers. The results showed higher levels of Maillard related processing markers in pre-hydrolyzed LHM compared with post-hydrolyzed LHM and conventional UHT milk which, on the other hand, contained higher concentrations of DHA-derived cross-links. Proteomics of collected particles from asymmetrical flow field-flow fractionation (AsFlFFF) in combination with gel electrophoresis indicated presence of intra-micellar cross-links during storage, for especially larger particles involving αS1- and αS2-caseins.

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BACKGROUND: Nε-carboxymethyllysine (CML), Nε-carboxyethyllysine (CEL) and α-aminoadipic acid (AAA) are important foodborne hazards and their intake can cause a variety of diseases in humans. It is extremely important to investigate the formation mechanism of CML, CEL and AAA, as well as their association with each other when aiming to control their production. RESULTS: A multi-response kinetic model was developed within the glucose-lysine Maillard reaction model system. The concentrations of glucose, lysine, glyoxal (GO), methylglyoxal (MGO), CML, CEL and AAA were quantified at different temperature (100-160 °C) and at different intervals (0-60 min). The experimental data were fitted to the proposed model to calculate kinetic parameters for the corresponding steps. The results indicated that the production of CML was primarily relied on the direct oxidative cleavage of the Amadori product, rather than the reaction between GO and Lys, whereas CEL and AAA were generated through the reaction of MGO with Lys. Significantly, the reaction between α-dicarbonyl compounds and Lys preferentially generated CML and CEL, resulting in the lower concentrations of AAA compared to CML and CEL. CONCLUSION: The multi-response kinetic model developed in the present study can be applied well to the Maillard reaction. The relationship between the formation mechanisms of CML, CEL and AAA is also explained. © 2024 Society of Chemical Industry.

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BACKGROUND: Melanoidins, as a functional component, exhibit antioxidant properties. However, the antioxidant mechanism of melanoidins in fish sauce remains poorly understood. The present study focused on the structural characteristics, microstructure and antioxidant activity of melanoidin substances in fish sauce. RESULTS: Ultrafiltration and color difference analysis were utilized to confirm the main molecular weight composition of melanoidins. The ultrafiltration component > 10 kDa in fish sauce exhibited the darkest and reddest color, along with the highest content of melanoidins (699.5 mg g-1). The spectral characteristics were consistent with typical melanoidins. Gas chromatography-tandem mass spectrometry and Fourier transform infrared spectroscopy analyses revealed that the melanoidins contained a significant number of oxygen-containing groups, amino compounds, carbohydrates, aromatic compounds and carbonyl compounds (CO), pyrrole (CN), among others. In total, 129 alkanes, 71 esters, nine olefins and two alkynes were identified. The melanoidins (> 10 kDa component) had the strongest antioxidant activity, including a reducing power of 0.8, 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) radical scavenging activity of 67.7% and 2,2-diphenyl-1-picrylhydrazyl radical scavenging activity of 92.4%. Additionally, the melanoidins (> 10 kDa component) had the highest total phenolic content at 48.2 µg gallic acid equivalents mL-1. CONCLUSION: Melanoidins are important factors affecting the antioxidant activity of fish sauce. There were differences in the structural properties of melanoidin fractions with different molecular weights. © 2024 Society of Chemical Industry.

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This study investigated the efficacy of glycation with edible uronic acid-containing oligosaccharides via the Maillard reaction to enhance the anti-inflammatory effect of fish myofibrillar protein (Mf). Lyophilized Mf was reacted with pectin oligosaccharide (PO, half of the total protein weight) at 60 °C and 35 % relative humidity for up to 12 h to produce glycated Mf (Mf-PO). After pepsin and trypsin digestion, the anti-inflammatory effect was assessed by measuring the secretions of proinflammatory cytokines in LPS-stimulated RAW 264.7 macrophages, and the anti-inflammatory effect of Mf was enhanced by PO-glycation without marked lysine loss and browning. The effects on the expressions of genes related to the LPS-stimulated signaling pathway in macrophages were also examined. PO-glycation suppressed LPS-stimulated inflammation by suppressing expression of cd14 and enhancing suppressive effect of Mf on the TLR4-MyD88-dependent inflammatory signaling pathway. Therefore, as an edible reducing sugar, PO could be an effective bioindustrial material for developing anti-inflammatory Mf.

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This study investigated the impact of processing temperatures (190 °C, 210 °C, and 230 °C) and durations (7 min, 10 min, and 14 min) on the formation of Maillard reaction products (MRPs) and antioxidant activities in pan baked buns. Key Maillard reaction indicators, including glyoxal (GO), methylglyoxal (MGO), 5-hydroxymethylfurfural (5-HMF), melanoidins, and fluorescent advanced glycation end products (AGEs) were quantified. The results demonstrated significant increases in GO, MGO, 5-HMF contents (p < 0.05), and antioxidant activities (p < 0.05) when the buns were baked at 210 °C for 14 min, 230 °C for 10 min and 14 min. However, the interior MRPs of baked buns were minimally affected by the baking temperature and duration. Prolonged heating temperatures and durations exacerbated MRPs production (43.8 %-1038 %) in the bottom crust. Nonetheless, this process promoted the release of bound phenolic compounds and enhanced the antioxidant activity. Heating induces the thermal degradation of macromolecules in food, such as proteins and polysaccharides, which releases bound phenolic compounds by disrupting their chemical bonds within the food matrix. Appropriate selections of baking parameters can effectively reduce the formation of MRPs while simultaneously improve sensory quality and health benefit of the pan baked buns. Considering the balance between higher antioxidant properties and lower MRPs, the optimal thermal parameters for pan baked buns were 210 °C for 10 min. Furthermore, a normalized analysis revealed a consistent trend for GO, MGO, 5-HMF, fluorescent AGEs, and melanoidins. Moreover, MRPs were positively correlated with total contents of phenolic compounds, ferric-reducing antioxidant power (FRAP), and color, but negatively correlated with moisture contents and reducing sugars. Additionally, the interaction between baking conditions and Maillard reactions probably contributed to enhanced primary flavors in the final product. This study highlights the importance of optimizing baking parameters to achieve desirable MRPs levels, higher antioxidant activity, and optimal sensory attributes in baked buns.

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Advanced glycation end products (AGEs) are a heterogeneous group of compounds formed both endogenously and exogenously through reactions between reducing sugars and amino acids within the proteins. The digestive tract may also serve as a site for endogenous AGEs generation. This study examined whether additional AGEs are formed during the digestion of glycated protein diets and meal-resembling systems (dietary proteins with fructose or glyoxal). The digestion of glycated protein showed that free AGEs were gradually released, but no additional AGEs were generated. In contrast, co-digestion of dietary proteins with fructose or glyoxal resulted in the formation of additional AGEs, and the reaction substrates (fructose or glyoxal) were depleted during digestion. Additionally, the lysine released from proteins decreased, leading to a loss of nutritional value of the food during co-digestion. The formation of AGEs and the depletion of essential amino acids in the gut may have significant implications for human health.

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Acrylamide (AA) is a contaminant resulting from the Maillard reaction and classified by the International Agency for Research on Cancer (IARC) as a probable carcinogen in Group 2A, with proven neurotoxic effects on humans. European Union (EU) Regulation No. 2017/2158 is currently in force, which establishes measures meant to reduce AA levels in food and sets reference values, but not legal limits, equal to 40 and 150 µg/kg AA in processed cereal-based foods intended for infants and young children and in biscuits and rusks, respectively. For this reason, sixty-two baby foods were analyzed using ultra-high performance liquid chromatography with diode array detector and quadrupole time-of-flight mass spectrometry (UHPLC-DAD-Q-TOF/MS) to check whether industries were complying with these values, even though AA control is not legally mandatory. In total, 14.5% of the samples exceeded the reference values; these were homogenized chicken products (211.84 ± 16.53, 154.32 ± 12.71, 194.88 ± 7.40 µg/kg), three biscuits (276.36 ± 0.03, 242.06 ± 0.78, 234.78 ± 4.53 µg/kg), a wheat semolina (46.07 ± 0.23 µg/kg), a homogenized product with plaice and potatoes (45.52 ± 0.28 µg/kg), and a children's snack with milk and cocoa (40.95 ± 0.32 µg/kg). Subsequently, the daily intake of AA was estimated, considering the worst-case scenario, as provided by the consumption of homogenized chicken products and biscuits. The results are associated with margins of exposure (MOEs) that are not concerning for neurotoxic effects but are alarming for the probable carcinogenic effects of AA.

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The organic selenium (Se), particularly in the form of selenoamino acids, in non-edible sections or by-products of Se-enriched plants, has the potential to generate Maillard reaction products (MRPs) during thermal treatment or fermentation. To elucidate the recycling process of organic selenium in foods and improve the utilization rate of Se, the biotransformation of organic selenium was studied by the cultivation of edible radish sprouts with Se-MPRs. Maillard reactions were simulated using selenoamino acids (SeAAs; selenomethionine and methylselenocysteine) and reducing sugars (glucose and fructose) for preparing Se-MRPs. The structures of the possible dehydrated Se-MRPs were analyzed using a HPLC-ESI-MS/MS system based on their fragmentation patterns and Se isotopic characteristics. Se absorption by the radish sprouts cultivated using Se-MRPs was estimated by the corresponding Se in the SeAAs and the total Se contents. The capabilities of SeAA transformation and total Se assimilation by the sprouts were related to the substrate composition during the Se-Maillard reaction. A particular Se-MRP (selenomethionine + fructose) increased SeAAs transformation by 33.8% compared to selenomethionine. However, glucose and fructose seemed to inhibit the transformation of the Se-MRPs to SeAAs by 10.0 to 59.1% compared to purified Se-MRPs. These results provide key references for the efficient utilization of organic Se in the cultivation of Se-enriched sprouts.

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As a protein extracted from soybeans, soy protein isolate (SPI) may undergo the Maillard reaction (MR) with co-existing saccharides during the processing of soy-containing foods, potentially altering its structural and functional properties. This work aimed to investigate the effect of mono- and polysaccharides on the structure and functional properties of SPI during MR. The study found that compared to oat ß-glucan, the reaction rate between SPI and D-galactose was faster, leading to a higher degree of glycosylation in the SPI-galactose conjugate. D-galactose and oat ß-glucan showed different influences on the secondary structure of SPI and the microenvironment of its hydrophobic amino acids. These structural variations subsequently impact a variety of the properties of the SPI conjugates. The SPI-galactose conjugate exhibited superior solubility, surface hydrophobicity, and viscosity. Meanwhile, the SPI-galactose conjugate possessed better emulsifying stability, capability to produce foam, and stability of foam than the SPI-ß-glucan conjugate. Interestingly, the SPI-ß-glucan conjugate, despite its lower viscosity, showed stronger hypoglycemic activity, potentially due to the inherent activity of oat ß-glucan. The SPI-galactose conjugate exhibited superior antioxidant properties due to its higher content of hydroxyl groups on its molecules. These results showed that the type of saccharides had significant influences on the SPI during MR.

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The role of the Maillard reaction and the accumulation of non-enzymatic glycation compounds in human milk have been scarcely considered. In this study, we investigated the proteins most susceptible to glycation, the identity of the corresponding modified residues and the quantitative relationship between protein-bound and free glycation compounds in raw human milk and, for comparison, in minimally processed infant formula and pasteurized bovine milk. In human milk, total protein-bound lysine modifications were up to 10% of the counterparts in infant formula, while Nε-carboxymethyllysine reached up to 27% of the concentration in the other two products. We demonstrated that the concentration of free pyrraline and methylglyoxal-hydroimidazolone were of the same order of magnitude in the three milk types. Our results delineate how the occurrence of some glycation compounds in human milk can be an unavoidable part of the breastfeeding and not an exclusive attribute of infant formulas and pasteurized bovine milk.

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This study used glycine (Gly), glucose (Glu), and soybean meal phytic acid (PA) as raw materials to investigate the effect of different PA addition amounts on the Gly-Glu Maillard reaction system and the antioxidant capacity of the products through rheological properties, particle size, chromatography, and other methods. The results showed that with the addition of PA, the apparent viscosity and average particle size of the system decreased, the thermal denaturation temperature increased, the product concentration decreased, the color became brighter, and the antioxidant performance was enhanced. This indicates that PA reacts with Gly and Glu to form PA - Gly and PA - Glu complexes, respectively, and hinders the Maillard reaction. This work demonstrates the potential application value of soybean meal PA in controlling the Maillard reaction.

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The removal of husks before the mashing process, also known as the Kubessa method, is an established brewing practice often positively associated with smoothness and better flavor-stability of beer. Empirical evidence on the effect of the Kubessa method on beer, however, has been lacking. Similarly, our study's comprehensive analysis of established brewing attributes revealed that traditional methods do not fully capture the impact of husk separation in beer brewing. Conclusive evidence of the Kubessa method's impact on beer aging chemistry was obtained through ultrahigh resolution mass spectrometry (FT-ICR-MS), revealing intricate molecular details inaccessible to conventional analytical techniques. The compositional information on thousands of molecules in Kubessa beer was resolved and compared to whole malt mashing. Machine learning algorithms applied to aging experiments identified over 500 aging-related compounds inhibited by husk separation. Complementary Time of flight mass spectrometry (ToF-MS) coupled with chromatography further confirmed that the mashing of husks introduces sulfur-containing lipid compounds. These significant differences in the beer composition provide valuable insights for further investigation into the staling protective effect of husk-separation (Kubessa process) during beer production, as empirically demonstrated in this work.

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The dynamic changes in volatile organic compounds (VOCs), reducing sugars, and amino acids of Dictyophora rubrovalvata (DR) at various drying temperatures were analyzed using GC-IMS, HPLC, and LC-MS. Orthogonal partial least squares discriminant analysis (OPLS-DA) combined with VOCs indicated that drying temperature of 80 °C was optimal. Variable importance in the projection (VIP) and relative odor activity value (ROAV) were employed to identify 22 key VOCs. The findings suggested that esters played a predominant role among the VOCs. Pearson correlation analysis revealed that serine (Ser), glutamine (Gln), lysine (Lys), alanine (Ala), threonine (Thr), glutamic acid (Glu), asparagine (Asn), ribose, and glucose were closely associated with the formation of esters, aldehydes, ketones, pyrimidines, and pyrazines. In conclusion, this study laid a foundational theory for elucidating the characteristics aroma substances and their production pathways, providing a valuable reference for analysing the flavor characteristics of DR.

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Mechanochemistry by milling has recently attracted considerable interest for its ability to drive solvent-free chemical transformations exclusively through mechanical energy and at ambient temperatures. Despite its popularity and expanding applications in different fields of chemistry, its impact on Food Science remains limited. This review aims to demonstrate the specific benefits that mechanochemistry can provide in performing controlled glycation, and in "activating" sugar and amino acid mixtures, thereby allowing for continued generation of colors and aromas even after termination of milling. The generated mechanical energy can be tuned under specific conditions either to form only the corresponding Schiff bases and Amadori compounds or to generate their degradation products, as a function of the frequency of the oscillations in combination with the reactivity of the selected substrates. Similarly, its ability to initiate the Strecker degradation and generate pyrazines and Strecker aldehydes was also demonstrated when proteogenic amino acids were milled with glyoxal.

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BACKGROUND: The Maillard reaction involves the interaction of various amino acids and reducing sugars, resulting in food browning. It often produces appealing aromas and flavors. The complexities of the reaction are such that it can be challenging to identify the often numerous and frequently volatile products formed by it. In the present study, we sought to identify and evaluate an unusual product with anti-oxidant activity arising from a fructose-histidine Maillard reaction model. The anti-oxidant profile of this product was assessed by computational means. RESULTS: The fructose-histidine Maillard reaction products (FH-MRPs) were generated by heating a 2:1 mixture of the sugar and the amino acid at 140 °C for 2 h. Chromatographically separable fractions, labelled DM-1 to DM-8, were obtained using silica gel as the stationary phase and dichloromethane/methanol (DCM/MeOH) mixtures as the mobile one. Fraction DM-5 exhibited the highest 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activity, and further bio-assay guided fractionation led to isolation and identification of 1-(1H-imidazo[4,5-c]pyridin-4-yl)ethenone (IMPE) as the active principal, the structure of which was established by nuclear magnetic resonance (NMR) spectroscopic and mass spectral techniques. A mechanism for the formation of IMPE from its precursors is proposed. Density functional theory (DFT) calculations suggest this novel heterocyclic compound exerts its anti-oxidant effects by interacting with DPPH and 2,2'-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radicals. Essentially, IMPE was non-toxic below 300 ug mL-1, showing a concentration-dependent free radical clearance capacity and reducing power within the 100-1000 µg mL-1 range, and moreover, exhibiting significant Fe2+ chelating abilities wihin the 50-200 µg mL-1 range. CONCLUSION: This study identified the unique FH-MRP, IMPE, and found that it acts as food antioxidant through the chelation of metal ions. © 2024 Society of Chemical Industry.

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The formation pathway and mechanism of various pyrazines were investigated during the thermal treatment of the alanine-xylose Amadori compound (Ala-ARP) and exogenous alanine (Ala). 15N-labeled Ala was used to coheated with Ala-ARP to clarify the nitrogen sources and the respective contributions of exogenous Ala and the regenerated Ala released from Ala-ARP to different pyrazine formation. It was found that exogenous Ala exhibited a priority in capturing glyoxal (GO) to form pyrazine during the thermal degradation of ARP. Compared to the Ala-methylglyoxal (MGO) model, a lower activation energy was required for the Ala-GO reaction, where the reaction dynamics of Ala-GO followed a zero-order model. In addition to forming pyrazine, the interaction between existing exogenous Ala and GO would accelerate the thermal degradation of Ala-ARP and retro-aldolization reaction of deoxyxylosones (DXs) to α-dicarbonyls. During this process, the release of regenerated Ala and MGO was promoted. Accordingly, as GO was expended by exogenous Ala during the initial stage of ARP-Ala degradation, the condensation between regenerated Ala and MGO became intensified, leading to the generation of methylpyrazine and 2,5-dimethylpyrazine. As a result, in the thermally treated mixture of Ala-ARP and exogenous Ala, 55% of the formed pyrazine originated from exogenous Ala, while 63% of the formed methylpyrazine and 57% of the formed 2,5-dimethylpyrazine were derived from regenerated Ala (120 °C, 30 min).

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Roasting is essential for developing the characteristic aroma of flaxseed oil (FSO), yet its impact on oil quality remains underexplored. This study employed headspace-gas chromatography-mass spectrometry coupled with multivariate analysis to elucidate the dynamic changes in volatile compounds and quality characteristics of FSO subjected to varying roasting temperatures. Our findings revealed that seven key aroma compounds, identified through the variable importance in the projection scores of partial least square-discrimination analysis models and relative aroma activity value, served as molecular markers indicative of distinct roasting temperatures. These compounds included 2,5-dimethylpyrazine, 2-pentylfuran, (E)-2-pentenal, 2-ethyl-3,6-dimethylpyrazine, heptanal, octanal, and 2-hexenal. Notably, roasting at 200°C was found to enhance oil stability and antioxidant capacity, with phenolic compounds and Maillard reaction products playing synergistic roles in bolstering these qualities. Network analysis further uncovered significant correlations between these key aroma compounds and quality characteristics, offering novel perspectives for assessing FSO quality under diverse roasting conditions. This research not only enriched our understanding of the roasting process's impact on FSO but also provided valuable guidance for the optimization of industrial roasting practices. This study would provide important practical applications in aroma regulation and process optimization of flaxseed oil. .

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This study was conducted to formulate a conjugate of soy protein isolate (SPI) and peach gum (PG) with improved functional properties, interacting at mass ratios of 1:1, 1:2, 1:3, 2:1, and 2:3 by Maillard reaction via wet heating method. Conjugation efficiency was confirmed by grafting degree (DG) and browning index (BI). Results indicated that DG increased with increasing concentration of PG, and decreased with increasing pH, whereas no remarkable change was observed with increasing reaction time. The conjugates were optimized at a ratio of 1:3. SDS-PAGE confirmed conjugate formation, Fourier transform infrared spectroscopy (FTIR) and circular dichroism (CD) verified conjugate secondary structural changes, and scanning electron microscopy (SEM) indicated significant overall structural changes. The functional properties, solubility, emulsifying stability, water holding, foaming, and antioxidant activity were significantly improved. This study revealed the wet heating method as an effective approach to improve the functional properties of soy protein.

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Increased production of advanced glycation end products (AGEs) among reducing sugars (glucose, fructose, galactose, or ribose) and amino acids/proteins via non-enzymatic Maillard reaction can be found in lifestyle-related disease (LSRD), metabolic syndrome (MetS), and obesity and immune-related diseases. Increased serum levels of AGEs may induce aging, diabetic complications, cardiovascular diseases (CVD), neurodegenerative diseases (NDD), cancer, and inflamm-aging (inflammation with immunosenescence). The Maillard reaction can also occur among reducing sugars and lipoproteins or DNAs to alter their structure and induce immunogenicity/genotoxicity for carcinogenesis. AGEs, as danger-associated molecular pattern molecules (DAMPs), operate via binding to receptor for AGE (RAGE) or other scavenger receptors on cell surface to activate PI3K-Akt-, P38-MAPK-, ERK1/2-JNK-, and MyD88-induced NF-κB signaling pathways to mediate various pathological effects. Recently, the concept of "inflamm-aging" became more defined, and we have unveiled some interesting findings in relation to it. The purpose of the present review is to dissect the potential molecular basis of inflamm-aging in patients with diabetes and immune-mediated diseases caused by different AGEs.

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Advanced glycation end products (AGEs) are complex and heterogeneous compounds closely associated with various chronic diseases. The changes in Nε-carboxymethyllysine (CML), Nε-carboxyethyllysine (CEL), Nε-(5-hydro-5-methyl-4-imidazolon-2-yl)-ornithine (MG-H1), and fluorescent AGEs (F-AGEs) in fried shrimp during frying (170 °C, 0-210 s) were described by kinetic models. Besides,the correlations between AGEs contents and physicochemical indicators were analyzed to reveal their intrinsic relationship. Results showed that the changes of four AGEs contents followed the zero-order kinetic, and their rate constants were ranked as kCML < kCEL ≈ kMG-H1 < kF-AGEs. Oil content and lipid oxidation were critical factors that affected the AGEs levels of the surface layer. Protein content and Maillard reaction were major factors in enhancing the CML and CEL levels of the interior layer. Furthermore, the impact of temperature on the generation of CML and CEL was greater than that of MG-H1 and F-AGEs.

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